EP3655452B1 - Polyuréthanes silylés et leurs procédés de préparation - Google Patents

Polyuréthanes silylés et leurs procédés de préparation Download PDF

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Publication number
EP3655452B1
EP3655452B1 EP18705624.7A EP18705624A EP3655452B1 EP 3655452 B1 EP3655452 B1 EP 3655452B1 EP 18705624 A EP18705624 A EP 18705624A EP 3655452 B1 EP3655452 B1 EP 3655452B1
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Prior art keywords
general formula
silylated polyurethane
group
polyol
polyisocyanate
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German (de)
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EP3655452A1 (fr
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Jan-Erik DAMKE
Johann Klein
Esteban Mejia
Rok BRISAR
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/809—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints

Definitions

  • the present invention relates to silylated polyurethanes obtainable by reacting at least one polyol, at least one polyisocyanate, and at least one silicon-containing heterocycle of the general formula (I) as defined herein and their preparation methods, curable compositions comprising the silylated polyurethane and their use as adhesive, sealant, spray foam and/or coating.
  • silane-modified adhesives and sealants have the advantage of being free from isocyanate groups, in particular monomeric diisocyanates, and they are also distinguished by a broad spectrum of adhesion on a wide range of substrates without surface pretreatment with primers.
  • polymers having reactive alkoxysilyl groups are capable of condensing with one another even at room temperature, eliminating alcohol molecules.
  • this causes mainly long-chain polymers (thermoplastics), relatively coarse-meshed three-dimensional networks (elastomers) or highly crosslinked systems (thermosets) to form.
  • Aminoalkoxysilanes are frequently used in adhesive formulations as polymer endcapping agents for moisture curable compositions.
  • Various aminoalkoxysilanes used for endcapping polymers are disclosed in US Patent 3632557 , 6162938 , 5364955 among others.
  • the resulting functional group from the reaction of amine with isocyanate-terminated polymers is urea.
  • Urea linkage serves as an important group in the adhesive formulations due to its stability and hydrophilic character.
  • its ability to form strong hydrogen bonds significantly increases the viscosity of the prepolymer after the endcapping.
  • the influence of hydrogen bonding in polyurethanes is investigated in depth in by Wilkes et al. ( Sami, S.; Yildirim, E.; Yurtsever, M.; Yurtsever, E.; Yilgor, E.; Yilgor, I.; Wilkes, G. L.; Polymer, 2014. 55(18): p. 4563-4576 ).
  • the object of the present invention is therefore to provide silane-modified polymers which solves some of the drawbacks of the known systems.
  • the object is achieved by introducing silicon-containing heterocycles of the general formula (I) as described herein.
  • the alkoxy adducts of cyclic silanes having one alkoxide residue may lead to up to 33% less expelled alcohol compared to aminoalkyltrimethoxysilane while showing a comparable curing speed.
  • the introduction of the silicon-containing heterocycle of the general formula (I) lowers the viscosity of the prepolymer due to their diminished propensity towards hydrogen bond formation.
  • the silicon-containing heterocycle of the general formula (I) is considerably less reactive, allowing a better reaction control and higher storage stability.
  • the present invention provides a silylated polyurethane obtainable by reacting:
  • the present invention also provides methods for preparing a silylated polyurethane by reacting at least one polyol having a number average molecular weight of from 1000 to 50,000 g/mol, at least one polyisocyanate, and at least one silicon-containing heterocycle of the general formula (I) as defined herein.
  • the present invention further relates to a curable composition
  • a curable composition comprising the silylated polyurethane according to the present invention and use thereof as adhesives, sealants, spray foam and/or coatings.
  • the present invention also provides an adhesive, sealant, spray foam and/or coating comprising the curable composition according to the present invention.
  • At least one means 1 or more, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, or more. With reference to an ingredient, the indication refers to the type of ingredient and not to the absolute number of molecules. "At least one polymer” thus means, for example, at least one type of polymer, i.e., that one type of polymer or a mixture of several different polymers may be used.
  • C 1 -C 20 alkyl or “C 1 -C 8 alkyl” residue refers to a monovalent group that contains from 1 to 20 or from 1 to 8 carbons atoms, that is a radical of an alkane and includes linear and branched organic groups.
  • alkyl residues include, but are not limited to: methyl; ethyl; propyl (or n-propyl); isopropyl; n-butyl; isobutyl; sec-butyl; tert-butyl; n-pentyl; n-hexyl; n-heptyl; and, 2-ethylhexyl.
  • alkyl residues may be unsubstituted or may be substituted with one or more substituents such as halo, preferably fluoro, nitro, cyano, amido, amino, preferably tertiary amino, sulfonyl, sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, and sulfamide.
  • substituents such as halo, preferably fluoro, nitro, cyano, amido, amino, preferably tertiary amino, sulfonyl, sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, and sulfamide.
  • halo preferably fluoro, nitro, cyano, amido, amino, preferably tertiary amino, sulfonyl, sulfinyl,
  • unsubstituted alkyl residues containing from 1 to 6 carbon atoms C 1 -C 6 alkyl
  • unsubstituted alkyl residues containing from 1 to 4 carbon atoms C 1 -C 4 alkyl
  • C 4 -C 8 cycloalkyl is understood to mean a saturated, mono- or bicyclic hydrocarbon residue having from 4 to 8 carbon atoms.
  • Examples of cycloalkyl residues include, but are not limited to: cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; and norbornane.
  • an "C 6 -C 18 aryl" residue is used alone or as part of a larger moiety - as in "aralkyl residue” - refers to optionally substituted, monocyclic, bicyclic and tricyclic ring systems in which the monocyclic ring system is aromatic or at least one of the rings in a bicyclic or tricyclic ring system is aromatic.
  • the bicyclic and tricyclic ring systems include benzofused 2-3 membered carbocyclic rings.
  • Exemplary aryl residues include, but are not limited to: phenyl; indenyl; naphthalenyl, tetrahydronaphthyl, tetrahydroindenyl; tetrahydroanthracenyl; and, anthracenyl.
  • a phenyl residue is preferred.
  • C 1 -C 20 alkylene or "C 1 -C 8 alkylene” residue refers to a divalent group that contains from 1 to 20 or 1 to 8 carbon atoms, that is a radical of an alkane and includes linear, branched organic or cyclic groups, which groups may be unsubstituted or substituted and may optionally be interrupted by at least one heteroatom.
  • the expression "interrupted by at least one heteroatom” means that the main chain of a residue comprises, as a chain member, at least one atom that differs from carbon atom, preferably selected from oxygen, sulfur, or nitrogen.
  • the present invention provides a silylated polyurethane obtainable by reacting:
  • polyol is understood for purpose of the present invention as a polymer having at least two hydroxyl groups.
  • a large number of polymers carrying at least two hydroxyl groups such as polyester polyols, polycaprolactones, polybutadienes or polyisoprenes as well as hydrogenation products thereof, or also polyacrylates or polymethacrylates, can be used as polyol. Mixtures of different polyols can also be used.
  • a polyether polyol is preferably used as the polyol.
  • a "polyether” is understood for purpose of the present invention as a polymer whose repeating unit contains ether functionalities C-O-C in the main chain. Polymers having lateral ether groups, such as cellulose ethers, starch ethers, and vinyl ether polymers, as well as polyacetals, are therefore not covered by this definition.
  • Polymers which contain polyethers as backbone have a flexible and elastic structure with which compositions that have outstanding elastic properties can be manufactured.
  • Polyethers are not only flexible in their backbone, but also strong at the same time.
  • polyethers in contrast to e.g., polyesters
  • polyethers are not attacked or decomposed by water and bacteria.
  • the polyol is a polyoxyalkylene, in particular polyethylene oxide and/or polypropylene oxide.
  • Polyethers that have been modified by vinyl polymers are also suitable for use as a polyol component. Products such as these are obtainable, for example, by polymerizing styrene and/or acrylonitrile, or a mixture thereof, in the presence of polyethers.
  • the polyol has a polydispersity (PD) of less than 2, preferably less than 1.5, and more preferably less than 1.3.
  • the number average molecular weight M n is understood as the arithmetically averaged molecular weight of the polymer.
  • the number average molecular weight M n is determined by gel permeation chromatography (GPC, also known as SEC) with tetrahydrofuran (THF) as the eluent according to DIN 55672-1:2007-08, preferably at 35°C. This method is known to one skilled in the art.
  • the ratio M w /M n also referred to as "polydispersity,” indicates the width of the molecular weight distribution and thus the differing degrees of polymerization of the individual chains in polydisperse polymers. For many polymers and polycondensates, the applicable polydispersity value is approximately 2. Strict monodispersity would exist for a value of 1. A low polydispersity (for example, less than 1.5) indicates a comparatively narrow molecular weight distribution and thus the specific expression of properties associated with molecular weight, for example viscosity.
  • polyoxyalkylene polymers that possess a narrow molecular weight distribution, and therefore a low polydispersity, are used as polymeric backbones. These can be manufactured, for example, by so-called double metal cyanide catalysis (DMC catalysis). These polyoxyalkylenepolymers are notable for a particularly narrow molecular weight distribution, a high average molecular weight, and a very small number of double bonds at the ends of the polymer chains. Polyoxyalkylene polymers of this kind have a polydispersity PD of at most 1.7.
  • organic backbones are, for example, polyethers having a polydispersity from approximately 1.01 to approximately 1.3, in particular approximately 1.05 to approximately 1.18, for example approximately 1.08 to approximately 1.11.
  • the polyol has a number average molecular weight (M n ) of from 1000 to 50,000 g/mol, preferably from 4000 to 30,000 g/mol, more preferably from 4000 to 25,000 g/mol.
  • M n number average molecular weight
  • the polyol has a number average molecular weight (M n ) of from 12,000 to 18,000 g/mol is particularly preferred.
  • Commonly used polymers are polyoxymethylene homo- and copolymers, polyurethanes, vinyl butyrates, vinyl polymers, e.g. polymers containing vinyl chloride and/or vinyl acetate, rayon, ethylene copolymers such as e.g. ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylate copolymers, organic rubbers, mixtures of different silylated polymers, such that the backbone can also contain silyl groups.
  • Examples include polyethers based on ethylene oxide, propylene oxide, and tetrahydrofuran, polyacrylate, and polymethacrylate.
  • polyethers and polyurethanes are preferred.
  • Polymers that contain polyethers as a backbone exhibit a flexible and elastic structure in the polymer backbone. Compositions that exhibit outstanding elastic properties can be manufactured therewith.
  • Polyethers are not only flexible in their framework, but also at the same time strong. For example, they are not attacked or decomposed by water and bacteria and are therefore notable for relative stability (in contrast to polyesters) with respect to environmental influences.
  • the polymer made up of an organic backbone having carbon atoms in the main chain, contained in the silane-crosslinking adhesive or sealant according to the present invention, does not include inorganic polymers such as, for example, polyphosphates, polysilanes, polysiloxanes, polysulfides.
  • inorganic polymers such as, for example, polyphosphates, polysilanes, polysiloxanes, polysulfides.
  • the polyisocyanates suitable for the present invention are preferably diisocyanate or triisocyanate, more preferably diisocyanate. They can be selected from ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,4-tetramethoxybutane diisocyanate, 1,6-hexamethylene diisocyanate (HDI), cyclobutane 1,3-diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate, bis (2-isocyanatoethyl) fumarate, as well as mixtures of two or more thereof, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4- and 2,6-hexahydrotoluoylene diisocyanate, hexahydro-1,3- or -1,4-phenylene diisocyanate, benz
  • trivalent or higher-valence isocyanates such as those obtainable, for example, by oligomerization of diisocyanates, in particular by oligomerization of the aforementioned isocyanates.
  • trivalent and higher-valence polyisocyanates are the triisocyanurates of HDI or IPDI or mixtures thereof, or mixed triisocyanurates thereof, as well as polyphenylmethylene polyisocyanate as obtainable by phosgenation of aniline-formaldehyde condensation products.
  • R 1 is hydrogen
  • R 2 and R 3 are same or different and are, independently from one another, selected from a linear or branched, substituted or unsubstituted C 1 -C 20 alkyl or C 6 -C 18 aryl residue, preferably selected from a C 1 -C 8 alkyl residue, more preferably a methyl, ethyl or propyl residue, which may be interrupted by at least one heteroatom
  • R 4 is selected from a linear or branched, substituted or unsubstituted C 1 -C 20 alkylene residue, preferably a C 1 -C 8 alkylene, more preferably a methylene, ethylene, 1,3-propylene, 2-methyl-1,3-propylene, or 1,4-butylene residue, most preferably a methylene or 1,3-propylene residue, in particular a 1,3-propylene residue, which may be interrupted by at least one heteroatom
  • R 5 and R 6 are same or different and are, independently from
  • R 1 is hydrogen;
  • R 2 is selected from a linear or branched, substituted or unsubstituted C 1 -C 8 alkyl residue;
  • R 3 is selected from a linear or branched, substituted or unsubstituted C 1 -C 8 alkyl residue;
  • R 4 is selected from a linear or branched, substituted or unsubstituted C 1 -C 8 alkylene residue;
  • R 5 is selected from hydrogen and a linear or branched, substituted or unsubstituted C 1 -C 8 alkyl residue while R 6 is selected from a linear or branched, substituted or unsubstituted C 1 -C 8 alkyl residue or a phenyl, or R 5 and R 6 form a 4- to 8-membered alkyl ring, in particular a 5- or 6-membered alkyl ring.
  • n is 2;
  • R 1 is hydrogen;
  • R 3 is selected from a methyl, ethyl or propyl residue, most preferably a methyl residue;
  • R 4 is selected from a methylene, ethylene, 1,3-propylene, 2-methyl-1,3-propylene, or 1,4-butylene residue, more preferably a methylene or 1,3-propylene residue, most preferably a 1,3-propylene residue;
  • R 5 is hydrogen; and/or R 6 is selected from a linear or branched, substituted or unsubstituted C 1 -C 8 alkyl residue or phenyl residue, or R 5 and R 6 form a 5- or 6-membered alkyl ring.
  • a preferred silicon-containing heterocycle of the general formula (I) for use in the present invention is selected from the group consisting of:
  • the silylated polyurethane according to the present invention has a viscosity of from 5 to 1000 Pa ⁇ s, preferably from 5 to 500 Pa ⁇ s, more preferably from 5 to 100 Pa ⁇ s, measured at 25 °C by Anton Paar MCR 302 Rheometer in neat conditions using PP25/TG stirring plate.
  • the silicon-containing heterocycle compound of the general formula (I) is obtainable by a one-step reaction of at least one epoxide compound of the general formula (II) and at least one aminoalkoxysilane having a primary amino group in the presence of a catalyst wherein R 5 and R 6 are the same as defined for the general formula (I) above.
  • Examples of the epoxide of the general formula (II) include, but are not limited to: ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxyhexane, 1,2-epoxydodecane, cyclohexyl oxirane, n-butyl glycidyl ether, tert-butyldimethylsilyl glycidyl ether, benzyl glycidyl ether, 10,11-epoxyundecan-1-ol, 4,5-epoxypentyl butyrate, 5,6-epoxyhexanenitrile, N,N-dimethyl-10,11-undecylamide, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, (2,3-epoxypropyl)benzene, styrene oxide, and 1,2,7,8-diepoxyoctane, chloro-2,3-e
  • the aminoalkoxysilane used in preparing silicon-containing heterocycle of the general formula (I) has the general formula (III) wherein, R 1 to R 4 are the same as defined for the general formula (I) above; and n is 0, 1, 2 or 3, preferably 3.
  • the aminosilane is aminoalkylenealkoxysilane. More preferably, the aminoalkylenealkoxysilane is selected from the group consisting of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltriisopropoxysilane, gamma-aminopropylmethyldiisopropoxysilane, alpha-aminomethyltriethoxysilane, alpha-aminomethyltrimethoxysilane, alpha-aminomethyldiethoxymethylsilane, alpha-aminomethyldimethoxymethylsilane, alpha-aminomethyltriisopropoxysilane, alpha-aminomethyldiisopropoxymethylsilane,
  • the synthesis of silicon-containing heterocycles of the general formula (I) may be conducted at a broad range of temperatures, e.g., from -100 to 50°C, preferably from 0 to 50°C, more preferably from 0 to 35°C, most preferably from 10 to 25°C such as at a room temperature.
  • the at least one epoxide is added in stoichiometric amounts or in an excess ranging from 1 to 200 %, preferably from 10 to 100 %, more preferably 50 %, with respect to the amino groups of the aminoalkoxysilane(s).
  • the unreacted epoxides are removed after the reaction using high vacuum.
  • the reaction is carried out in at least one neat or in dry solvent.
  • solvents include, but are not limited to: toluene, acetonitrile, tetrahydrofuran, ethylene glycol, diethyl ether, dimethyl ether, benzene, ethyl acetate, isopropanol, propanol, ethanol, methanol, chloroform, chloromethane, dichloromethane, pentane, hexane, heptane, cyclohexane, isooctane, toluene, xylene, dioxane, butyl acetate, acetonitrile or dimethylformamide. Mixtures of different solvents can also be used.
  • Reaction times may vary from 0.5 to 96 hours, preferably from 2 to 48 hours.
  • the one-step reaction for preparing the silicon-containing heterocycle of the general formula (I) is carried out in the presence of a catalyst.
  • a catalyst include, but are not limited to: Lewis acid or base catalysts or Br ⁇ nsted-Lowry acid or base catalysts or a combination thereof.
  • Lewis acid catalysts more preferably weak Lewis acid catalysts can be used.
  • Lewis acid refers to any electrophilic reagent that is capable of accepting an electron pair, but not a proton like it is in the case of Br ⁇ nsted-Lowry acid.
  • week Lewis acid refers to an electron pair acceptor which forms a strong conjugate base.
  • the acidity of a metal based Lewis acids decrease with a growing a metal radius (e. g. Al>Fe>Ca). Therefore the term weak Lewis acid is associated to the acids containing elements like Ca, Mg, Na, etc.
  • the week Lewis acid shows a pKa value of ⁇ 8 ( Jander et al., combined analyses:
  • the Lewis acid portion of the catalyst includes an element selected from Groups 1 to 14 of the Periodic Table or contains a lanthanide metal.
  • Useful Lewis acids may either be neutral (e.g., compounds such as AlCl 3 , CrCl 2 , CrCl 3 , ZnCl 2 , BF 3 , BCl 3 , Yb(OTf) 3 , FeCl 2 , FeCl 3 , CoCl 2 , etc.) or cationic.
  • a broad array of metallic Lewis acids have been found be applicable in the present invention.
  • metal is an alkaline earth metal of Group 2, such as magnesium, calcium, beryllium, strontium.
  • organocalcium, organomagnesium, organostrontium or organoberyllium compounds are preferred, wherein these metal catalysts comprise preferably alkoxy groups, sulfonate groups, carboxyl groups, dialkyl phosphate groups, dialkyl pyrophosphate groups and/or diketonate groups.
  • Particularly suitable catalyst is selected from calcium bistrifluoroacetate, calcium bisacetate, calcium bispivalate, calcium bisisobutyrane, calcium bispropionate, calcium acetate, calcium benzoate, calcium cyclohexanecarboxylate, calcium 2,2-difluoroacetate, calcium 2-fluoroacetate, calcium 2-chloroacetate, calcium methyl carbonate, magnesium bistrifluoroacetate, magnesium bisacetate, magnesium bispivalate, magnesium bisisobutyrane, magnesium bispropionate, magnesium acetate, magnesium benzoate, magnesium cyclohexanecarboxylate, magnesium 2,2-difluoroacetate, magnesium 2-fluoroacetate, magnesium 2-chloroacetate, and magnesium methyl carbonate.
  • Transition metals can also be used in the reaction according to the present invention.
  • the transition metal is aluminum, chromium, indium or gallium.
  • an organotitanate is used as the catalyst.
  • the organotitante include, but are not limited to: titanium(IV) complex compounds with two 1,3-diketonate ligands, in particular 2,4-pentane dionate (acetylacetonate), and two alcoholate ligands; titanium(IV) complex compounds with two 1,3-ketoesterate ligands, in particular ethyl acetoacetate, and two alcoholate ligands; titanium(IV) complex compounds with one or more amino alcoholate ligands, in particular triethanolamine or 2-((2-aminoethyl)amino)ethanol, and one or more alcoholate ligands; titanium(IV) complex compounds with four alcoholate ligands; as well as more highly condensed organotitanates, in particular oligomeric titanium(IV) tetrabutanolate, also referred to as polybutyl titanate; wherein, as alcoholate ligands, iso
  • Tyzor® AA GBA, GBO, AA-75, AA-65, AA-105, DC, BEAT, BTP, TE, TnBT, KTM, TOT, TPT or IBAY (all from Du Pont/Dorf Ketal); Tytan PBT, TET, X85, TAA, ET, S2, S4 or S6 (all from TensoChema) and Ken-React® KR® TTS, 7, 9QS, 12, 26S, 33DS, 38S, 39DS, 44, 134S, 138S, 133DS, 158FS or LICA® 44 (all from Kenrich Petrochemicals).
  • Nitrogen-containing Lewis or Br ⁇ nsted-Lowry bases can also be used.
  • these catalysts include, but are not limited to: 1,4-diazabicyclo[2.2.2]octane, N,N,N',N'-tetramethyl alkylenediamines, polyoxyalkylenamines, triethylamine, tripropylamine, trimethylamine, as well as amidines, such as, in particular, 6-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN); guanidines such as, in particular, tetramethylguanidine, acetylacetoneguanidine, 2-guanidinobenzimidazole, 2-tert.butyl-1,1,3,3-tetramethylguanidine, 1,3-
  • the catalyst can be added up to 10 mol%, preferably from 0.01 to 10 mol%, more preferably from 0.5 to 5 mol%, most preferably from 1 to 2.5 mol%, relative to the mol% of the amine functionality of the aminoalkoxysilane.
  • the present invention provides a method for preparing a silylated polyurethane by reacting:
  • the silicon-containing heterocycle of the general formula (I) can be added to NCO-terminated prepolymer(s) or can be blended with polyisocyanate(s) prior to the reaction with polyol(s).
  • the silylated polyurethane is obtainable by
  • a stoichiometric excess of the NCO group of the polyisocyanate(s) with respect to the OH group of the polyol(s) used is preferably equal to 1.01 to 2.0, more preferably 1.05 to 1.5. This ensures that NCO-terminated polyurethane prepolymers are formed as a reaction product.
  • the thereby obtained NCO-terminated polyurethane prepolymer is then reacted with at least one silicon-containing heterocycle of the general formula (I) to obtain the silylated polyurethane according to the present invention, which preferably comprises alkoxysilyl groups as reactive end groups.
  • the silicon-containing heterocycle of the general formula (I) is used for each isocyanate group of the polyurethane prepolymer.
  • the silicon-containing heterocycle of the general formula (I) is used at a slight stoichiometric excess.
  • the above-described embodiments can be performed under the following conditions.
  • at least one polyol and at least one isocyanate functional compound (polyisocyanate) are mixed together for 0.5 to 5 hours at temperature from -10 to 150°C, preferably from 25 to 100°C.
  • at least one silicon-containing heterocycle of the general formula (I) is added as endcapper.
  • Suitable reaction temperature is in a range between -10 and 150°C, preferably between 25 and 100°C, more preferably between 60 and 90°C.
  • Reaction time largely depends on the selected isocyanate functional compound, endcapper and catalyst employed and is in range from 1 to 72 hours, preferably from 6 to 12 hours. The above reactions are usually preformed without using a solvent.
  • solvents can be used.
  • Useful solvents are acetone, butanone, ethyl acetate, toluene, acetonitrile, tetrahydrofuran and ethylene glycol dimethyl ether, hexane, heptane, pentane, cyclohexane and benzene.
  • the silylated polyurethane is obtainable by
  • a stoichiometric excess of the NCO group of the polyisocyanate(s) with respect to the amino group of the silicon-containing heterocycle(s) of the general formula (I) used is preferably equal to 1.1 to 3.0, more preferably 1.5 to 2.5.
  • At least one silane compound of the general formula (I) and at least one isocyanate functional compound (polyisocyanate) are mixed together for 0.1 to 5 hours at temperature from -10 to 150°C, preferably from 0 to 80°C.
  • at least one polyol is added to the NCO-terminated endcapper.
  • Suitable reaction temperature is in a range between -10 and 150°C, preferably between 25 and 100°C, more preferably between 60 and 90°C.
  • Reaction time largely depends on the selected isocyanate functional compound, endcapper and catalyst employed and is in range from 1 to 72 hours, preferably from 6 to 12 hours.
  • the reaction for forming a NCO-terminated endcapper is usually preformed without using a solvent.
  • solvents can be used.
  • Useful solvents are acetone, butanone, ethyl acetate, toluene, acetonitrile, tetrahydrofuran and ethylene glycol dimethyl ether, hexane, heptane, pentane, cyclohexane and benzene.
  • the silylated polyurethane according to the present invention is obtainable by one-pot synthesis by blending at least one polyol having a number average molecular weight of from 1000 to 50,000 g/mol, at least one polyisocyanate, preferably diisocyanate, and at least one silicon-containing heterocycle of the general formula (I) as described herein.
  • reaction progress can be monitored using infrared spectroscopy (IR).
  • IR infrared spectroscopy
  • aforementioned methods for preparing a silylated polyurethane further comprises a step of adding at least one catalyst.
  • Suitable catalysts are organometallic Lewis acids like iron or tin compounds, in particular the 1,3-dicarbonyl compounds of iron or of di- or tetravalent tin, tin(II) carboxylates or dialkyltin(IV) dicarboxylates, or the corresponding dialkoxylates, e.g., dibutyltin dilaurate (DBTL), dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctoate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate, dibutyltin diiosooctylmaleate, dibutyltin ditridecylmaleate, dibutyltin dibenzylmaleate, dibutyltin maleate, dibutyltin diacetate, tin (II)
  • alkyl titanates such as tetrabutyl titanate and tetrapropyl titanate
  • organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminum ethylacetoacetate
  • chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate, lead octanoate, organosilicon titanium compounds, or bismuth tris-2-ethylhexanoate
  • acid compounds such as phosphoric acid, p-toluenesulfonic acid, or phthalic acid
  • aliphatic amines such as butylamine, hexylamine, octylamine, decylamine, or laurylamine
  • aliphatic diamines such as, ethylenediamine, hexyldiamine, or also aliphatic poly
  • tin compounds di(n-butyl)tin(IV) sulfide, di(n-butyl)tin(IV) oxide, di(n-octyl)tin(IV) oxide, (n-butyl) 2 Sn(SCH 2 COO), (n-octyl) 2 Sn(SCH 2 COO), (n-octyl) 2 Sn(SCH 2 CH 2 COO), (n-octyl) 2 Sn(SCH 2 CH 2 COOCH 2 CH 2 OCOCH 2 S), (n-butyl) 2 Sn(SCH 2 COO-i-C 8 H 17 ) 2 , (n-octyl) 2 Sn(SCH 2 COO-i-C 8 H 17 ) 2 , (n-octyl) 2 Sn(SCH 2 COO-n-C 8 H 17 ) 2 .
  • Chelate-forming tin organyls can also be used, for example di(n-butyl)tin(IV) di(acetylacetonate), di(n-octyl) tin(IV) di(acetylacetonate), (n-octyl)(n-butyl)tin(IV) di(acetylacetonate).
  • Tin-free catalysts are also particularly preferred.
  • Boron halides such as boron trifluoride, boron trichloride, boron tribromide, boron triiodide, or mixed boron halides, can thus furthermore be used as curing catalysts.
  • Boron trifluoride complexes such as, for example boron trifluoride diethyl etherate ( CAS no. [109-63-71 ]), which, as liquids, are easier to handle than the gaseous boron halides, are particularly preferred.
  • Lewis bases can be used like: trimethylamine, triethylamine, triphenylborane, triphenylphosphine, 1,8-diazabicycloundec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,8-bis(tetramethylguanidino)naphthalene, 2- tert -butyl-1,1,3,3-tetramethylguanidine, phosphazene base P 4 - t -Bu, phosphazene base P 1 -t-Bu-tris(tetramethylene), phosphazene base P 2 -Et, pho
  • the present invention provides a curable composition comprising at least one silylated polyurethane according to the present invention or obtainable by the aforementioned methods according to the present invention.
  • a "curable composition” is understood to be a substance or mixture of multiple substances, which is curable by physical or chemical measures.
  • these chemical or physical measures can be, for example, the supplying of energy in the form of heat, light, or other electromagnetic radiation, but also simply bringing into contact with atmospheric moisture, water, or a reactive component.
  • the composition thereby changes from an original state to a state that has a higher hardness.
  • the composition also contains at least one compound which has a hydrolysable silicon-containing group and a weight average molecular weight in the range of 100 to 1000 g/mol measured by GPC according to DIN 55672-1:2007-08.
  • This compound is used as a crosslinking agent, and in addition to the hydrolysable silicon-containing group may contain further functional groups.
  • the compound may be a silane coupling agent.
  • This type of coupling agent may be used as a tackifier, as an agent which influences the physical properties, as a drying agent, as a dispersion aid, or as a filler or the like.
  • a silane coupling agent can act as an adhesion promoter and increase the adhesion to various surfaces, for example glass, aluminum, stainless steel, zinc, copper, mortar, PVC, acrylic resins, polyester, polyethylene, polypropylene, and polycarbonate.
  • Such a silane coupling agent may include reactive silicon-containing groups which may be defined analogously to the groups described above in conjunction with polymer component a).
  • the groups may also be those of formula (IV): -(Si(R 7 ) 2-e (Y) e -O) k -Si(R 7 ) 3-d Y d (IV), where R 7 is selected from a hydrocarbon residue containing 1 to 20 carbon atoms or a triorganosiloxane group of formula -O-Si(R 8 ) 3 , where each R 8 is independently selected from a hydrocarbon residue containing 1 to 20 carbon atoms; each Y is independently selected from a hydroxy group or a hydrolysable group, preferably an oxime group or alkoxy group; and k is 0, 1, or 2; e is 0, 1, or 2 and d is 0, 1, 2, or 3, where d and e are both not 0, and k is 0 or an integer from 1 to 19, where d is not 0 when k is 0.
  • Compound of formula (IV) may contain further functional groups, including but not limited to primary, secondary, or tertiary amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurate groups, halogens, and the like.
  • these coupling agents include but are not limited to silanes containing isocyanate groups, such as gamma-isocyanate propyltrimethoxysilane, gamma-isocyanate propyltriethoxysilane, gamma-Isocyanate propylmethyldiethoxysilane, gamma-isocyanate propylmethyldimethoxysilane, (isocyanate methyl)trimethoxysilane, (isocyanate methyl)methyldimethoxysilane, (isocyanate methyl)triethoxysilane, and (isocyanate methyl)diethoxymethylsilane; silanes containing amino groups, such as gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltriisopropoxysilane, gamma-aminopropylmethyld
  • Aminosilanes selected from the group consisting of bis(trimethylsilyl)amine, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, bis[(3-triethoxysilyl)propyl]amine, bis[(3-trimethoxysilyl)propyl]amine, aminopropylmethyldiethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane, phenylaminomethyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, 3-( N -phenylamino)propyltrimethoxysilane, 3-piperazinylpropylpropyltrimethoxysilane, 3-piperazinylpropylpropyl
  • Examples of compounds of formula (IV) which contain no additional functional groups include tetraalkoxysilanes (tetraalkylsilicates), such as tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-isopropoxysilane, tetra-n-butoxysilane, tetra-isobutoxysilane, and tetra- t -butoxysilane; trialkoxysilanes, such as methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, and phenyltrimethoxysilane; dialkoxy
  • the curable composition can also contain, in addition to the aforementioned silylated polyturethane according to the present invention, adjuvants and additives, such as catalysts, plasticizers, stabilizers, antioxidants, fillers, reactive diluents, drying agents, adhesion promoters and UV stabilizers, fungicides, flame retardants, rheological adjuvants, color pigments or color pastes, and so on.
  • adjuvants and additives such as catalysts, plasticizers, stabilizers, antioxidants, fillers, reactive diluents, drying agents, adhesion promoters and UV stabilizers, fungicides, flame retardants, rheological adjuvants, color pigments or color pastes, and so on.
  • plasticizer is understood as a substance that decreases the viscosity of the compositions and thus facilitates processability. Hydrophilic plasticizers serve to improve moisture uptake and thus to improve reactivity at low temperatures. Suitable as plasticizers are, for example, adipic acid esters, azelaic acid esters, benzoic acid esters, butyric acid esters, acetic acid esters; esters of higher fatty acids having approximately 8 to approximately 44 carbon atoms, esters of OH-group-carrying or epoxidized fatty acids, fatty acid esters and fats, glycolic acid esters, phosphoric acid esters, phthalic acid esters of linear or branched alcohols containing 1 to 12 carbon atoms, propionic acid esters, sebacic acid esters, sulfonic acid esters, thiobutyric acid esters, trimellitic acid esters, citric acid esters, and esters based on nitrocellulose and polyvinyl acetate, as well as mixture
  • Plasticizers can be additionally used in the composition at between 0 and 40 wt%, by preference between 0 and 20 wt%, based on the total weight of the composition.
  • Stabilizers for purposes of this invention are to be understood as antioxidants, UV stabilizers, or hydrolysis stabilizers. Examples thereof are the commercially usual sterically hindered phenols and/or thioethers and/or substituted benzotriazoles and/or amines of the hindered amine light stabilizer (HALS) type. It is preferred in the context of the present invention if a UV stabilizer that carries a silyl group, and that is incorporated into the end product upon crosslinking or curing, is used. The products Lowilite 75, Lowilite 77 (Great Lakes, USA) are particularly suitable for this purpose.
  • Benzotriazoles benzophenones, benzoates, cyanoacrylates, acrylates, sterically hindered phenols, phosphorus, and/or sulfur can also be added.
  • composition according to the present invention can contain up to 2 wt%, by preference 1 wt% of stabilizers, based on the total weight of the composition.
  • composition according to the present invention can further contain up to 7 wt%, in particular up to 5 wt% of antioxidants, based on the total weight of the composition.
  • the catalysts that can be used are all known compounds that can catalyze hydrolytic cleavage of the hydrolysable groups of the silane groupings, as well as subsequent condensation of the Si-OH group to yield siloxane groupings (crosslinking reaction and adhesion promotion function).
  • titanates such as tetrabutyl titanate and tetrapropyl titanate
  • tin carboxylates such as dibutyltin dilaurate (DBTL), dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctoate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate, dibutyltin diiosooctylmaleate, dibutyltin ditridecylmaleate, dibutyltin dibenzylmaleate, dibutyltin maleate, dibutyltin diacetate, tin octaoate, dioctyltin distearate, dioctyltin dilaurate (DOTL), dioctyltin diethylmaleate, dioctyltin
  • the catalyst preferably mixtures of several catalysts, can be used in a quantity from 0.01 to 5 wt% based on the entire weight of the composition.
  • composition according to the invention may additionally contain fillers.
  • fillers Suitable examples here are chalk, lime powder, precipitated and/or pyrogenic silicic acid, zeolites, bentonites, magnesium carbonate, diatomaceous earth, alumina, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder, and other ground mineral substances.
  • organic fillers may also be used, in particular carbon black, graphite, wood fiber, wood flour, sawdust, cellulose, cotton, pulp, wood chips, chopped straw, and chaff.
  • short fibers such as glass fiber, glass filament, polyacrylonitrile, carbon fiber, Kevlar fiber, or also polyethylene fiber may be added.
  • Powdered aluminum is likewise suitable as filler.
  • the pyrogenic and/or precipitated silicic acids advantageously have a BET surface area of 10 to 90 m 2 /g. During use, they do not cause an additional increase in the viscosity of the composition according to the invention, but contribute to strengthening of the cured composition.
  • pyrogenic and/or precipitated silicic acids having a larger BET surface area, advantageously 100-250 m 2 /g, in particular 110-170 m 2 /g, as filler. Due to the larger BET surface area, the same effect, for example strengthening the cured composition, may be obtained at a lower weight fraction. Further substances may thus be used to improve the composition according to the invention with regard to other requirements.
  • hollow spheres having a mineral shell or a plastic shell are suitable as filler. These may be, for example, hollow glass spheres which are commercially available under the trade name Glass Bubbles®. Hollow spheres based on plastic, for example Expancel® or Dualite®, are described in EP 0520426 B1 , for example. These are composed of inorganic or organic substances, each having a diameter of 1 mm or less, preferably 500 ⁇ m or less.
  • fillers are preferred which impart thixotropy to the compositions.
  • Such fillers are also described as rheological aids, for example hydrogenated castor oil, fatty acid amides, or swellable plastics such as PVC.
  • rheological aids for example hydrogenated castor oil, fatty acid amides, or swellable plastics such as PVC.
  • a suitable dosing device a tube, for example
  • such compositions have a viscosity of 3000 to 15,000 mPa ⁇ s, preferably 40,000 to 80,000 mPa ⁇ s, or also 50,000 to 60,000 mPa ⁇ s.
  • the fillers are preferably used in a quantity of 1 to 80% by weight, based on the total weight of the composition.
  • Suitable pigments are titanium dioxide, iron oxides, or carbon black.
  • composition according to the present invention In order to enhance shelf life even further, it is often advisable to further stabilize the composition according to the present invention with respect to moisture penetration using drying agents. A need occasionally also exists to lower the viscosity of the adhesive or sealant according to the present invention for specific applications, by using a reactive diluent. All compounds that are miscible with the adhesive or sealant with a reduction in viscosity, and that possess at least one group that is reactive with the binder, can be used as reactive diluents.
  • polyalkylene glycols reacted with isocyanatosilanes e.g. Synalox 100-50B, Dow
  • isocyanatosilanes e.g. Synalox 100-50B, Dow
  • vinyltriethoxysilane phenyltrimethoxysilane, phenyltriethoxysilane, octyltrimethoxysilane, tetraethoxysilane, vinyldimethoxymethylsilane (XL12, Wacker), vinyltriethoxysilane (GF56, Wacker), vinyltriacetoxysilane (GF62, Wacker), isooctyltrimethoxysilane (IO)
  • Also usable as reactive diluents are the following polymers of Kaneka Corp.: MS S203H, MS S303H, MS SAT 010, and MS SAX 350.
  • Silane-modified polymers that are derived, for example, from the reaction of isocyanatosilane with Synalox grades can likewise be used.
  • silylated polyurethanes according to the present invention can be used in a mixture with usual polymers or prepolymers known per se, optionally with concurrent use of the aforementioned reactive diluents, fillers, and further adjuvants and additives.
  • "Usual polymers or prepolymers” can be selected in this context from polyesters, polyoxyalkylenes, polyacrylates, polymethacrylates, or mixtures thereof; these can be free of groups reactive with siloxane groups, but optionally can also comprise alkoxysilyl groups or hydroxyl groups.
  • a plurality of the aforementioned silane-functional reactive diluents have at the same time a drying and/or adhesion-promoting effect in the composition.
  • These reactive diluents may be used in quantities between 0.1 and 15 wt%, by preference between 1 and 5 wt%, based on the total weight of the composition.
  • adhesion promoters are so-called tackifying agents, such as hydrocarbon resins, phenol resins, terpene-phenolic resins, resorcinol resins or derivatives thereof, modified or unmodified resin acids or resin esters (abietic acid derivatives), polyamines, polyaminoamides, anhydrides, and anhydride-containing copolymers.
  • tackifying agents such as hydrocarbon resins, phenol resins, terpene-phenolic resins, resorcinol resins or derivatives thereof, modified or unmodified resin acids or resin esters (abietic acid derivatives), polyamines, polyaminoamides, anhydrides, and anhydride-containing copolymers.
  • tackifying agents such as hydrocarbon resins, phenol resins, terpene-phenolic resins, resorcinol resins or derivatives thereof, modified or unmodified resin acids or resin esters (abietic acid derivatives), polyamines, polyaminoamides, anhydr
  • tackifying agents are used as adhesion promoters, their nature and quantity depend on the adhesive/sealant composition and on the substrate onto which it is applied.
  • Typical tackifying resins such as, for example, terpene-phenolic resins or resin acid derivatives, may be used in concentrations between 5 and 20 wt%;
  • typical adhesion promoters such as polyamines, polyaminoamides, or phenolic resins or resorcinol derivatives may be used in the range between 0.1 and 10 wt%, based on the total weight of the composition.
  • the curable composition according to the invention is produced according to known methods by intimately mixing the components in suitable dispersion units, for example a high-speed mixer.
  • the present invention also provides the use of the curable composition comprising the silylated polyurethane according to the present invention as adhesives, sealants, spray foam and/or coatings.
  • a further field of application of the curable compositions according to the present invention is use as plugging, hole-filling, or spackling compound.
  • compositions according to the invention are thus suitable for adhesively bonding plastics, metals, glass, ceramic, wood, wood-based materials, paper, paper-based materials, rubber, and textiles, for gluing floors, sealing building elements, windows, wall and floor coverings, and jointing in general.
  • the materials in each case may be adhesively bonded to themselves or with any other of the stated materials.
  • IPDI isophorone diisocyanate
  • IPDI isophorone diisocyanate
  • IPDI isophorone diisocyanate
  • IPDI isophorone diisocyanate

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Claims (15)

  1. Polyuréthane silylé pouvant être obtenu en mettant en réaction :
    a) au moins un polyol ayant un poids moléculaire moyen en nombre de 1 000 à 50 000 g/mol ;
    b) au moins un polyisocyanate, de préférence un diisocyanate ; et
    c) au moins un hétérocycle contenant du silicium de formule générale (I)
    Figure imgb0023
    où R1 représente l'hydrogène ;
    R2 et R3 sont identiques ou différents et sont, indépendamment l'un de l'autre, choisis parmi un alkyle en C1 à C20 linéaire ou ramifié, substitué ou non-substitué, ou un résidu aryle en C6 à C18 qui peut être interrompu par au moins un hétéroatome ;
    R4 est choisi parmi un résidu alkylène en C1 à C20 linéaire ou ramifié, substitué ou non-substitué qui peut être interrompu par au moins un hétéroatome ;
    R5 et R6 sont identiques ou différents et sont, indépendamment l'un de l'autre, choisis dans le groupe constitué par l'hydrogène, un alkyle en C1 à C20 linéaire ou ramifié, substitué ou non-substitué ou un aryl en C6 à C18 qui peut être interrompu par au moins un hétéroatome, et un cycloalkyle en C4 à C8, ou R5 et R6 peuvent former un cycle, de préférence un cycle alkyle de 4 à 8 chaînons ; et
    n représente 0, 1, ou 2, de préférence 2.
  2. Polyuréthane silylé selon la revendication 1, l'hétérocycle contenant du silicium de formule générale (I) pouvant être obtenu par une réaction en une étape d'au moins un composé époxyde de formule générale (II) et au moins un aminoalcoxysilane ayant un groupe amino primaire en présence d'un catalyseur
    Figure imgb0024
     où R5 et R6 sont tels que définis pour la formule générale (I) ci-dessus.
  3. Polyuréthane silylé selon la revendication 2, l'aminoalcoxysilane ayant la formule générale (III)
    Figure imgb0025
     où R1 à R4 sont tels que définis pour la formule générale (I) ; et n représente 0, 1, 2 ou 3.
  4. Polyuréthane silylé selon l'une quelconque des revendications 1 à 3, le polyol étant un polyol de polyéther.
  5. Polyuréthane silylé selon l'une quelconque des revendications 1 à 4, n dans la formule générale (I) représentant 2 et n dans la formule générale (III) représentant 3.
  6. Polyuréthane silylé selon l'une quelconque des revendications 1 à 5, R3 étant choisi parmi un résidu alkyle en C1 à C8, de préférence méthyle, éthyle ou n-propyle.
  7. Polyuréthane silylé selon l'une quelconque des revendications 1 à 6, le polyuréthane silylé pouvant être obtenu en
    (a) mettant en réaction au moins un polyol ayant un poids moléculaire moyen en nombre de 1 000 à 50 000 g/mol avec au moins un polyisocyanate, de préférence un diisocyanate, avec un excès stœchiométrique du groupe NCO du ou des polyisocyanate(s) par rapport au groupe OH du ou des polyol(s) de façon à former un prépolymère de polyuréthane à terminaison NCO ; et
    (b) mettant en réaction ledit prépolymère de polyuréthane à terminaison NCO avec au moins un hétérocycle contenant du silicium de formule générale (I)
    Figure imgb0026
     où R1 à R6 et n sont tels que définis ci-dessus pour la formule générale (I).
  8. Polyuréthane silylé selon la revendication 7, un rapport molaire du groupe NCO de l'un ou des polyisocyanate(s) au groupe OH du ou des polyol(s) étant de 1,01 à 2,0.
  9. Polyuréthane silylé selon l'une quelconque des revendications 1 à 6, le polyuréthane silylé pouvant être obtenu en
    (a) mettant en réaction au moins un polyisocyanate, de préférence un diisocyanate, avec au moins un hétérocycle contenant du silicium de formule générale (I)
    Figure imgb0027
     où R1 à R6 et n sont tels que définis ci-dessus pour la formule générale (I), avec un excès stœchiométrique du groupe NCO du ou des polyisocyanate(s) par rapport au groupe amino du ou des hétérocycle(s) contenant du silicium de formule générale (I) ; et
    (b) mettant en réaction le produit de réaction obtenu à l'étape (a) avec au moins un polyol ayant un poids moléculaire moyen en nombre de 1 000 à 50 000 g/mol.
  10. Polyuréthane silylé selon la revendication 9, un rapport molaire entre le groupe NCO du ou des polyisocyanate(s) au groupe amino du ou des hétérocycle(s) contenant du silicium de formule générale (I) étant de 1,1 à 3,0.
  11. Procédé de préparation d'un polyuréthane silylé en mettant en réaction
    (a) au moins un polyol ayant un poids moléculaire moyen en nombre de 1 000 à 50 000 g/mol ;
    (b) au moins un polyisocyanate, de préférence un diisocyanate ; et
    (c) au moins un hétérocycle contenant du silicium de formule générale (I)
    Figure imgb0028
    où R1 représente l'hydrogène ;
    R2 et R3 sont identiques ou différents et sont, indépendamment l'un de l'autre, choisis parmi un alkyle en C1 à C20 linéaire ou ramifié, substitué ou non-substitué, ou un résidu aryle en C6 à C18 qui peut être interrompu par au moins un hétéroatome ;
    R4 est choisi parmi un résidu alkylène en C1 à C20 linéaire ou ramifié, substitué ou non-substitué qui peut être interrompu par au moins un hétéroatome ;
    R5 et R6 sont identiques ou différents et sont, indépendamment l'un de l'autre, choisis dans le groupe constitué par l'hydrogène, un alkyle en C1 à C20 linéaire ou ramifié, substitué ou non-substitué ou un aryl en C6 à C18 qui peut être interrompu par au moins un hétéroatome, et un cycloalkyle en C4 à C8, ou R5 et R6 peuvent former un cycle, de préférence un cycle alkyle de 4 à 8 chaînons ; et
    n représente 0, 1, ou 2, de préférence 2.
  12. Composition durcissable comprenant le polyuréthane silylé selon l'une quelconque des revendications 1 à 10 ou le polyuréthane silylé pouvant être obtenu par le procédé selon la revendication 11.
  13. Composition durcissable selon la revendication 12, la composition comprenant en outre au moins un composant choisi dans le groupe constitué par les plastifiants, stabilisants, antioxydants, charges, diluants réactifs, agents dessicatifs, promoteurs d'adhérence, agents anti-UV, agents rhéologiques, solvants, et des mélanges de ceux-ci.
  14. Adhésif, agent d'étanchéité, mousse pulvérisée et/ou revêtement comprenant la composition durcissable selon la revendication 12 ou 13.
  15. Utilisation de la composition durcissable selon la revendication 12 ou 13 en tant qu'adhésifs, agents d'étanchéité, mousse pulvérisée et/ou revêtements.
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